Manufacture of hydrogen



Oct. 20, 1953 w. B. JOHNSON 2,655,255

MANUFACTURE oF. HYDROGEN Filed Feb. 2, 1949 .www

Y I ATTORNEYS.

Patented Oct. 20, 1953 `UNITED STATES PATENT OFFICE Willam'B. Johnson, Far Hills, N. J., assignor to `The M. W. `Kellogg Company, Jersey City, N. J., a corporation of Delaware Application February 2, 1949, Serial N o. 74,213

v13 Claims.

This invention relates to the manufacture of hydrogen. In one aspect this invention relates to the manufacture of substantially pure hydrogen from solid carbon containing materials, such as coal, coke and shale', and from hydrocarbons. One of the most costly features in connection with coal gasication as proposed todayis the removal ofcarbon dioxide from the product gas to raise its heating value or to enrich thegas with hydrogen to produce a gas suitable for the Fischer-Tropsch reaction. Presently proposed systems contemplate coal gasification with steam and oxygen, shifting of the carbon monoxide content with steam to produce carbon dioxide and hydrogen and the nal removal of carbon dioxide. An additional disadvantage of coal gasication is that in most instances substantially pure oxygen is recommended inbrder to eliminate the large amount of nitrogen as a diluent inthe product gas. The above disadvantages are also to some extent present in the production of hydrogen or hydrogen 'containing gases from hydrocarbons. The process of the present invention is directed to a method for the production of hydrogen employing a contact material suspended inthe reaction mixturecin a novel manner which eliminates or minimizeslthe aforesaid difficulties in the presently proposed methods.

'I'he object of this invention is to produce P substantially pure hydrogen. I l

Another object of this inventionfis to'produce hydrogen from solid carbon containing materials'.` Still another object of this invention: isfto provide la process for the production of hydrogen; from hydrocarbons, particularly relatively-,high boiling hydrocarbons such as reduced crudes normally undesirable for conversion torhydrogen.

It is another object of this inventiontojprovide a process for the production of a suitable Fischer-Tropsch gas mixture and the `conversionthereof to hydrocarbons and oxygenated organic compounds. Y. y

` It s a further object of the present inventionV to. produce hydrogen from carbon containing materials without the necessity for the removal of carbon dioxide or nitrogen from the product` gas. Y

Yet another and further object 4is to provide come apparent to those skilled inthe art .from

the accompanying description and disclosure.

(c1. ca -214) According to this invention, a gas rich `in carbon monoxide is produced in a conventional manner such as the gasiiication of coal by partial oxidation. The carbon monoxide is reacted Withfa particular metal oxide to be discussed more fully hereinafter under exothermic conditions such that the metal oxide is reduced to a lower oxide or to theelementary metal by Vsuspension in nely-divided form in the carbon monoxide reactant. Appropriate conditions of temperature and contact time are employed to Vobtain the desired reduction of the metal oxide and to substantially completely convert all of the carbon monoxide to carbon dioxide. Carbon dioxide and any `diluents or contaminants of the original carbon monoxide feed mixture are removed from the Areaction involving the reduction of the metal loxide and discarded. The reduced metal oxide which, as previously stated,A may be in the `form of a lower metal oxide or the elementary metal is passed from the reduce tion step to an oxidation step in which the reduced metal oxide is reacted with steam While suspended in finely-divided form in the steam reactant under endothermic conditions such that the reduced -metal oxide is oxidized and steam is converted to hydrogen. Appropriate conditions of temperature and' contact time lare employed to obtain the required oxidation of the reduced `material and to' convert the desired proportionl of the steam. Substantially pure hydrogen is removed from the oxidation step and recovered Vby condensing the steam accompanying the hydrogen eiuent. The oxidized materialfrom the oxidation step is returned to the reduction step to complete the cycle.

wIn the process of this invention the metal of the contact material is chosen by the fact that its reduction with carbon monoxide is exothermic and its oxidation with steam is endothermic whereby the step involving the reduction of the -metal oxide will liberate a sulicient amount of heat together with the sensible heat supplied thereto by preheating the reactants so that this heat may be employed to furnish sub'- stantially al1 of the required amount of heat for the endothermic oxidation of the reduced metal with steam. `The transfer of heat is accomplished by recycling a sucient quantity of'contact material between the reaction zones at the temperature levels of these respective reaction zones such that a balanced heating system is obtained. Excess heat liberated in the reduction of` the metal oxide may be removed in a conventional manner, such as by indirect heat ex-A change with the cooling medium or by the direct injection of a vaporizable liquid into the reduction zone. Suitable metals and/or mixtures thereof which satisfy the requirement of being capable of liberating heat during their reduction and consuming heat during their oxidation comprise nickel, manganese, cobalt and vanadium. The preferred'metal employed in the process -of-the present invention zis manfganese and under the preferred operating conditions the higher oxide of manganese is reducedf` to a lower oxide of manganese rather thanY to` the elementary manganese.

According to the preferred embodimentof this: invention, the linear gas velocity'.ofithefigaseousf; reactant stream is passed upwardly through the reaction zone in the presence of thesuSpended.V

contact material at a Velocity between about 0.5 and about 6 feet per second suchJ th'at'thel.V

finely-divided contact material forms a so-called pseudo-liquid dense phase ofsolidsf-havingfaconcentration between aboutI 30 and.. aboutU 120 pounds of metal oxide perfcubic'iootfof gasf. This pseudo-liquid dense phase is characterized by the high-turbulency and internal circulation offthe solid particles within the densev phase.

The contact material is employed in a'iine state of subdivision. Preferably, thel powdered mate-I rial initially contains no more than -a minorl pro portion by weight of material whose particle. size is g-reater than about 250=microns- Preferably, also the greater proportionof the mass ofnely-divided material comprises material. whose particle size is smallerthan 100 microns,` preferably between about 20 and about 80 microns.- A highly desirable powdered oxide` of manganese for Vuse in this invention comprises about l per cent between -0 and 20 microns, about 20 per cent between and 40 microns, about. 30 percent between about 40 and 60 microns, about125 per cent between and 80 microns, and not over 10 per cent` above 80 microns.

In the preferred form of this invention, the powdered mass is maintained ina reactor substantially larger than the volume occupied :byr the mass itself in the fluidized condition. InV this operation all but a minor proportiony of the catalyst mass is contained in the dense' iiuidized pseudo-liquid mass which may be designated as the dense phase. lower portion. of the reactor while fthat part-of the reactor abo-ve the dense phase-is occuped'iby a mixture of gases and powdered'solids.inwhich the concentration of solids is much lowenandiof an entirely Vdifferent order of magnitude.' than the concentration'of solidsin the-dense phase; This' volume above the dense phase isf. designated as the dilute or. diffuse phase and-islconsidered to be a'disengaging zone iniwhichfsolids lifted above the dense phase by the upwardowing gask stream are disengaged therefrom and -returned to the dense phase to the extent thatfsuch solids are present in the diffuse phase in excess of the carrying capacity of the gas stream at the linear velocity of thatgas stream therein. As used herein, linear velocity is the. velocity at which the gas stream would pass'through the re'- action Zone in the absence of solid material. Between the dense phase of high average concentration and the diffuse phase of low average concentration there is a relatively narrow Zone in which the concentration of solidsV in ther gas stream changes in a short space from a high concentraticn of the high phase to the low concentration of the diffuse phase. This zone has the The dense phase occupies thel flO 4 appearance of an interface between two visually distinct phases.

Although the preferred embodiment of this invention constitutes eiecting the reactions in the presence of the pseudo-liquid dense phase of finely-divided solids, it is, however, within the scope of this invention to carry out the reactions in which the: gaseoussstream' passing through the-reaction'zonefis of "such ahigh velocity that the finely-divided contact material is entrained orfcarried in the gaseous stream and circulated infthedirection of flow of the gaseous stream through th'e reaction zone. As a result of the solids'fbeing.; circulated with the gas stream, the

"sol-idsflhave"aurelatively short residence time in thee reaction zone, being generally a matter of secondsfascompared to a matter of hours with dense phase operations in which the solids possess internal circulation. In this manner of operation, the so-called pseudo-liquid dense phase is notf-formedzbut thereisI acontinuous phase'of entrained forcarried solids in the vgaseous stream in thereactionrzonef Inorder to effect-the con-v tinuous circulation. or 'entrainment of the Asol-ids in :thegaseous streamlgas velocities -above about 6"-feet .per second are required, rusually between aboutlO and aboutf50 feetper second. At such highrgas velocities: at which the pseudo-liquid dense phase is'not formed but instead al continuous phasey is formed, the concentration ofsolids inthe gaseous stream ismuch lower than'that experienced .with thefpseudo-liquid dense. phase. In the highvelocity systemxthe concentration of solids in the gasrstreamzisless. than about 25` pounds per cubic foot of gas and usually; between about 3 anda-bout'l` pounds per cubic foot of gas; The actual concentration within .the vabove range will 'depend' upon such factors as gas velocity,v reactants,l type land size fof reactor,l etc.

As used herein, the suspension of `finely-divided solids-v ina; gaseousv streamv referswto either the highv velocity continuous fphase technique or` to the pseudo-liquid:densefvphase technique.

In'the'relatively 4low Velocity dense phase: operation; gasivelocities Aare ordinarily `employed vwhichr result .inzaz small proportion of the` solids bein-g' carriedi overhead from' the reaction zone with' the reaction eiliuent, and, as a consequence thereof, it is necessary to provide means in the 'rea'ce tor: itself or externally'for'. separating suchentrained solids and returningthem to the:- dense phase.; Whennoperatingwith a relativelyhigh velocity continuous phase,A separation'meansmust be provided for removing the bulk of the solids fromzthefreaction:eiluent andreturning 'it to the reactionzone; also, means must be provided for recovering a small amount ofl entrained solids a-fterremoval of the bulk of the solids fromfthe effluent.. The recovered solids in either case may be returned to the reaction zone.

In al preferred modiation of this invention the metalliferous contact material, such as an oxidel off manganese, mayA be combined with a suitable conversion promoter or promoters by impregnating themanganese oxide with a minor amount of such a promoter or by introducing separate particles'of the promoter in admixture with the oxide of manganese into the reaction zone. Such promoters comprise iron, thoria, tungsten, copper, etc= It may also be desirable to vmaintain the metal oxide on a suitable inert material as asupport or carrier, or'it may be desirable vto have such inert material'present in they reaction zone itself as separate particles from the oxides of manganese, as a ydiluent. This inert materia-l may vserve as a heat carrier andalso may servek in aiding in the suspension and fluidization of the metal oxide. Such inert materialsy suitable as diluents or carriers comprise silica, alumina, magnesia, bentonite type clays as Filtrol and Super-Filtrol (acid treated bentonite), and various materials known to those skilled in the art. If present as separate rparticles in admixture with the oxygen carrier, the inert material is of a size within the ranges previously discussed with reference to the manganese oxide. The various metals suggested as appropriate contact `materials for this invention may be used alone or in combination with each other and in combination with promoters and supports. For example, acombination of manganese and cobalt oxides may be employed.

The controlling temperature of the process is the temperature employed in the reaction involving the oxidation of the reduced metalliferous material whereby steam is converted to hydrogen. This temperature depends primarily upon the rate of reaction and upon the equilibrium or conversion of steam to hydrogen. Since the conversion of steam to hydrogen in the presence of the metal oxides suggested for this invention is favored by relatively low temperatures, low temperatures are preferred; however, employing a very low Vtemperature results in such a slow rate of reaction that the process becomes commercially unfeasible. It is recommended that in general a temperature of below 1100" F. be employed in all instances to obtain an optimum equilibrium or conversion and yet a sufficiently high temperature to obtain an appropriate rate of reaction, When employing an oxide of manganese a temperature between about 800 and about 1100" F. is considered satisfactory from the standpoint of conversion and rate of reaction. Since the equilibrium and rate of reactionis not substantially affected by pressure lthe pressure employed usually will be that pressure desired for the product gas. i

The temperature conditions of the reduction step involving` the reduction of the oxidized contact material 'withcarbon monoxide will depend upon the temperature employed in the hydrogen producing step previously described.'` Since'the reduction of the particular metal oxides of this process with carbon monoxide is exothermic and itis a feature of this inventionvto employ ther heatthus liberated for supplying the necessary heat inthe hydrogen producing step, it isk prefA ferred to maintain the temperature at least 1007'` F. above the hydrogen producing step tempera-` ture. Preferably, the temperature of this latter stepis at least 200 F. above the hydrogen pro--l ducing step so that rapid heat transfer may be obtained between the nely-divided contact Vmaterial circulated between the exothermic and` endothermic reaction zones. Since the equilib-l rium for the' reduction of metalr oxide with carbon monoxide is favored in the direction of the consumption ofcarbon monoxide by relatively low temperatures, it is desirable to use as low a temperature as possible for this purpose.` In accordance with one modication of this `inven-' tion, two steps are employed for the reduction of the metal oxide with carbon monoxide. The first step employs a relatively high temperature in order to supply the required heat tothe hydrogen producing step or endotherrnic reaction zone and subsequently the unconverted carbon monoxide and unreduced'rnetal oxide from the rstwstep are subjected to a lower heat treatment in a second step at which the equilibrium is more favorable to the consumption of carbon monoxide. In this manner substantially complete utilization of the carbon monoxide is obtained. This feature of the invention will be more fully described in connection with the accompanying drawings to be hereinafter discussed. Any pressure may be employed on reduction of the metal oxide with carbon monoxides as this reaction is not materially iniiuenced by pressure.

It is within the scope of this invention to operate one reaction zone according to the high velocity continuous phase technique and to operate another reaction zone according to the relatively low velocity dense phase technique. For example, the endothermic reaction zone or hydrogen producing zone may be operated such that finelydivided solids are carried by entrainment in the gaseous reaction mixture and are removed together with the reaction mixture and products from that reaction zone and passed to a conventional solids separator, such as a cyclone separator. The solids removed from the eiliuent gases in the solids separator are then returned to the inlet to-the reaction zone, such as by means of astandpipe or a Fuller Kinyon pump, to be recycled through the reaction zone. The exothermic reaction zone or the zone in which the metal oxide is reduced with carbon monoxide may be operated simultaneously by the dense phase technique as previously discussed and rine-` ly-divided contact material circulated between the two reaction zones in the required amount and conventional manner.

The accompanying drawing is a diagrammatic illustration in elevation of an arrangement of apparatus for carrying out the process of this invention for `the production of substantially pure hydrogen from coal employing manganese as the contact material. The reaction conditions and specific illustrations given in the description of the drawing are those preferred and best suited for the process described, but should not be considered as unnecessarily limiting the invention. As the basis for better understanding of the present invention, the process of the drawing will be described with respect to the production of mols of hydrogen per hour. It is to be understood that although the drawing is limited to the production of hydrogen from coal the process of the present invention may apply to the production of hydrogen from light and heavy hydrocarbons, reduced crudes and high sulfur contentV conduit Il to blower I2 at which point it is compressed to` the desired pressure which will be somewhat higher than the pressure desired for the product gas.' About 62,000 cubic feet per hour of air are compressed to 50 pounds per square inch gage and passed through conduit I3 toa conventional slagging type producer I 4. Approximately 1,440 poundsper hour of coal or coke are introduced into producer I by means of inlet conduit I6. The gasification temperature of the producer is maintained between about 1800 and 'about 2200" F. Approximately 260 pounds per hour of liquid slag is removedv from tap holey I'I. Efliuent gas at a temperature of about -0 F. is removed from producer I4 and4 passed through conduit I8 to a steam superheater or heat exchanger I9 where the effluent is cooled ging producer is removed from heat exchangerV Component Mol Percent Excess coal is employed in producer il'. in order to minimize conversion of the coal to` carbon dioxide. Although the process has beendescrbed with the use of air, substantially pure oxygen may be employed in producer I. Sincel the present process has as one of its advantages` the use of air without the accompanying contamina'- tion of the product with nitrogen, the employment of oxygen is economically unfeasible.

About 230 mols per hour of eiliuent gas' containing carbon monoxide and' nitrogen is passed through conduit 24 to exother-mic reducing` chamber 26 in which it contacts a finely-divided oxide of manganese. contained therein in a pseudo-liquid fluidized condition in the form of a fluidbed, as shown. This reaction chamber is maintained at a temperature of about 1200'F. by the preheat of the feed gas and the exothermic nature of the reaction, such that metal oxides are reduced and carbon' monoxide is converted to carbon dioxide. LAt the temperature of reaction employedv in chamber 26 a substantial portion of the carbon monoxide remains unconverted, and, in orderr to substantiallycompletely convert this carbon monoxide, finely-divided manganese oxorder that sucient manganese oxide will be present in the second step to convert substantially all of the carbon monoxide and forA acting' as a heat carrier for transferring heat from reaction chamber 26 to the subsequent hydrogen producing step (chamber 41). A typical composition of the effluent gas from reaction chamber 26 is as follows:V

A typical compositionv of the' Component Mol Percent The effluent from chamber 26 of the above composition is withdrawn therefrom in an amount of 2,462 mols per hour through conduit 21 which contains an inlet above the interface in reactor 25, as shown. Gases are passed through conduit 21 to a heat exchanger or boiler 28 which cools the mixture of gases and entrained solids-from a temperature of about l200 F. to about 40`0 F. The velocity of the gaseous stream in conduit 21 is sufficiently high to entrain the contact material and continuously move it in the direction of flow of the gases upwardly through boiler 28 and conduit 29 to separator and reaction chamber 3 In conduit 29 the exothermic reaction of the carbon monoxide withV the metal oxide raises thetemperature to about 600 F. and the,v contact material settles to the bottom of. chamber 3|.. The feed to boiler 28 is adjusted to keep the maximum temperature obtained in conduit 29. below about '100 F. It is preferred to maintain theoutlet of conduit 29 adjacent to the bottomof chamber 3|, as shown. Contact material from cham.- ber 3| may be recirculated to conduit 21 bymeans of a conventional standpipe 32, thus assuring substantially complete conversion of. carbon.

monoxide and reduction of the metal oxide to the desired lower oxide. from chamberl 3| through conduit 33 and` is expanded at about 20 pounds per square inch gageand- 600 F. to atmospheric pressure through expander 34 to utilize the energy contained therein. Expander 34 may generate electricity for the process. eiiiuent to about 365 F. and the effluent thus expanded is vented to the atmosphere through1 stack 36. A typical composition of the eiuent' at this point is as follows:

Component Mol Percent The amount of gas vented through stack 36 is about 246 mols per hour.

About 3,400 pounds per hour of reducedv metal oxides from secondary reducing reactor`v 3| arepassed therefrom through conduit 31 to pri-mary reducing reactor 26. From primary reducing reactor 26 finely-divided reduced contact material is removed throughr standpipe 38 for passage to` oxidation or hydrogen producing reactor 411 where it is contacted with steam under endothermic conditions such that the reduced contact material is oxidized and hydrogen is produced. If' desired, substantially completely reduced contact material may be removed fromi secondary reducing reactor 3| through conduits 31 and 39' slmultaneously with removal of contact material from reactor 26 through conduitv 38, and' passed to reactor 41. Alternatively, all ofthe reduced contact material passed to reactor 41 may be obtained directly from reactor 3| byl removal through standpipes or conduits 31- and 39. Thischanged with the eiuent gases from slagging' producer I4, as previously discussed; The temperature of the steam entering superheater I9 is about 340 F. and the temperature :of the steamv leaving heat exchanger I9 through conduit'46isY about 1200 F. The quantity of steam at this point is about 3,600 pounds per hour since watery condensed from the eiiluent of reactor 41 is combined with the fresh feed water in conduit 40 bvV means of conduit 53.

An eiiluent is removed-v This reduces the temperature of thev Y this manner.

Steam at approximately 1200` F. is passed throughconduit 46 to oxidizing reactor 41. Ap-J proximately 62,600 pounds per hour. of manganese oxide are introduced into conduit 46 through conduit 38. from the bottom of reactor 26. The iinely-divided reduced metal oxide is suspended `in the steam and carried to the bottom of reactor 41. This quantity of metal oxide atthe temperature thereof and the temperature of the superheated steam assures a reaction temperature inreactor 41 of about 1000.F. The upward gas velocity in reactor 41 is suicientto maintain the iinely-divided contact material suspended in a pseudo-liquid iiuidized condition with an interface in the reactor, as shown. Since excess steam is employed the effluent in conduit 49 consists substantially of hydrogen and steam in a mol ratio of approximately 1:1. Reduced contact material is oxidized in reactor 41 and is ,removed from the bottom thereof by means of standpipe 48 and returned to the bottom of ,reducing reactor 26 by introduction into conduit 24. Approximately 64,200 pounds per hour of a higher oxide of manganese are returned by this means to reactor 26. In a modification, all or a portion of the contact materialv withdrawn from reactor 41 may be passed directly to reactor 3| by means not shown from where it is passed to reactor 26 through conduit 31.

The principal source of heat for the endothermic reaction effected in reactor A41 is the.

sensible heat of the circulated contact material from reactor 26. In the preferred embodiment of this invention, substantially all of the heat except that supplied by superheating the steam is supplied to reactor 41 from the hot'contact material from reactor 26. Nevertheless, it is within the scope of this invention to supply a minor proportion of the heat required for the endothermic in reactor 41 by other means such as indirect heat exchange with furnace gases or the direct in jection of hot gases intoreactor 41. 1 The eiiluent from reactor 41 comprising hydrogen and excess steam and free from nitrogen is discharged through conduit 49 and passed through heat exchanger 42 in which a portion of its heat is transferred to the incoming feed water. From heat exchanger 42 the eiiiuent is passed through condenser 5| in which the steam is. condensed and the cooled eiliuent is passed to an a'ccumulator 52. Water is Withdrawn from unit 52 through conduit 5'3 and circulated by'means yoi pump 54 to inlet feed line 40. About 1,800 pounds per hour of water are returned to the system in Hydrogen substantially free from water and other impurities is removed from accumulator 5-2 through conduit 56 atthe desire pressure as the product of the process. 1

` If it is desired to obtain hydrogen at substantially elevated pressures as the product of the process, an additional compressor may be positioned on conduit 24 to compress the reactant carbon monoxide to the desired pressure. The reaction chambers are operated at substantially the same pressures in order that standpipes may be employed for transferring contact material therebetween. However, the reactors may be operated at diierent pressures if desired by using other means for compressing the contact material, such as by a Fuller Kinyon pump.

In the case in which the carbon-containing material of the feed is natural gas or other hydrocarbon, the partial combustion thereof will result in the production of hydrogen and carbon monoxide. This hydrogen is utilized in theprocess in the reduction of the metal oxides in reactors 26 and 3| so that there is no loss of hydrogen in the system. In the use of a Santa Maria crude the sulfur which may be in the form of hydrogen sulfide or the oxide passes through reactors 26 and 3| without substantial impairment of the reactions being eiected therein; consequently, the process is particularly adaptable to the use of high sulfur crudes which ordinarily cannot be employed because of their sulfur content.

In the process of this invention the principal source of hydrogen is the conversion of steam in reactor l41 by means of reaction with the reduced contact material. It is also contemplated that the reaction of steam with a reduced contact material as described above is the sole source of hydrogen produced. Similarly, the principal source of the reducing gas for reducing the oxidized contact material in reactors 26 and 3| is carbon monoxide when a solid carbon containing material is the feed and carbon monoxide and hydrogen when a hydrocarbon is the feed.

In the event the hydrogen produced is employed as one of the reactants to make up the synthesis feed gas in the Fischer-Tropsch reaction, the carbon monoxide necessary for this feed may be produced in a separate producer (not shown) by the conversion of coal or coke with substantially pure oxygen or enriched air. The product in this step is substantially pure carbon monoxide free from nitrogen. This carbon monoxide `is then combined in the desired ratio with the hydrogen produced, as described previously, and the feed thus obtained is utilized under conventional conditions of temperature, pressure, contact time and catalyst to lproduce hydrocarbons and oxygenated organic compounds by the Fischer-Tropsch reaction. Making the FiScher-Tropsch feed gas in this manner rather than by partial combustion of hydrocarbons With pure eoxygen or by conversion of coal and steam with the required oxygen to maintain the desired temperature reduces the requirement of pure oxygen by about 50 per cent. 'The reduction of the required oxygen by this method is a substantial monetary saving in the synthesis process.

, Various modifications of the process and the apparatus employed may become apparent to those skilled in the art without departing from the scope of this invention. Certain pieces of apparatus, such as pumps, storage vessels, valves, conduits, recycle lines, etc., have been omitted from the drawing as a matter of clarity and convenience, and their location and use will be obvious to those skilled inthe art.

Having described my invention, I claim:

l. A process for producing hydrogen which comprises combusting carbon containing material with oxygen containing gas under conditions suitable for the production of a major proportion Aof carbon monoxide and a minor proportion of carbon dioxide, passing excess steam upwardly through an oxidizing zone in the presence of nely divided reduced metalliferous contact ma-l terial at a velocity eiective to suspend the contact material in a pseudo-liquid condition at a temperature below about 1100 F. but sufficiently high such that hydrogen is produced under endothermic conditions at a desired rate bythe reaction of steam with the contact material and the contact material is oxidized, passing oxidized contact material from the oxidizing zone to a first reduction zone, passing carbon monoxideV which is prepared from combustingcarhoncon;- taining material in excess upwardly through said first reduction zone at a velocity effective to suspend the oxidized contactr material in a pseudo'- liquid condition therein at a temperature significantly above the temperature of said oxidizing zone under exothermicconditions such-that themetalliferous contact material is reduced by theA carbon monoxide whichisconvertedlto carbon dioxide and the heat. generatedtherein is sufficient to constitute the principal sourceA of heat for. the oxidizing zone, passing a relatively small proportion ofcontact material from the rst reduction zone toa second reductionzone wherein the contact material is further reduced bythe unconverted carbon monoxide from the first reduction zone at a temperature below about 700i'F. but suiciently high to obtain the desired rate ofreaction, removing an eiiluentfromthe said second reduction zonecomprising carbon dioxide and substantially free of carbon monoxide, recycling reduce'dimetalliferous contact material to the said oxidizing zone lat a temperature and in an amount sufficient to constitute the principal source of heat thereto, at least a portion of the reduced contact material is. recycled from the first reduction zone, and recovering hydrogen from the oxidizing zone -astheV product. of. the process.

2. The process vof claim l whereinthe .carbon containing material is coal.

3; The processv ofclaim 1 wherein thev carbon containing m-aterial is a hydrocarbon. i '4.- The process of claim l whereinthev carbon containing -material is; a sulfurI bearing fcrude.

5 Theprocess oflclaim 1 wherein the carbon containing-material is a-shale.

6; A process for producing hydrogen from: coal which comprises the steps of combustingexcess coalwith airat a temperature between about 1800 and-about2200 F. under'conditions such that carbon monoxide'is'produced as amajor prod-uct and carbon dioxide is produced in only a minor proportion, passing' excess steam? upwardly through an oxidizing'zone `in the-presence -of fine ly-divided reducedmetalli-ferons material at a velocity' effectivestoA suspendfsaid nely-di'vided material in a pseudo-liquid condition at a temperature-below about 1100F. but sufficiently high suchthathydrogen--is produced under endothermic-conditions lat a desired rate by the reaction of steam with said contact vmaterial whereby the contact material is oxidized, passing oxidized contact material from said-oxidizing zone-toa first reductionV zone; passingv carbon monoxide produced.Y in said 'coalcombustio'nf step in excess upwardly through saidr'rst reduction. zone in the presence Aof finely-divided oxidized metalliferous contact material at av velocity effective: to suspendsaid'nely-divided contact material in a pseudo-liquid condition therein 1. at. a temperature at least 100. F: above. the temperature-of said oxidation zone under exothermic. conditions such that the metalliferous contact material is reduced by carbon monoxidewhich isconverted tolcarbon dioxide, removing fromsaidrst reduction zone an effluent contain-ing` a relatively small proportion of unconverted rcarbon monoxide and suspended contact material and passing same to aseparate-*second lowetemperature reduction zone in which the remaining unconverted carbon` monoxide fromsaid first reduction zone reduces unreduced metalliferouscontact material suspendedin.- the reaction-mixture atia temperature below.- Aabouti '10074 F.' but at 1a. suicientlyi nighg Cil temperature to obtainthe-desired rate ofreaction, recovering reduced metal oxideffrom said second'freductionzone vandreturning same to: said rstureductionf zone, removing an eiiiuentr. from said second-reductionzonelcomprisingzcarbon di.- oxide andisubstantiallyfree from carbon monoxide, passing reduced: metalliferous' contact' mate-f rialfr'om said rstfreduction zonexto said'oxidationfzone.- at. a-temperaturev and in an amounts'uf; cient'. to z constitute the principalrsourcev of :heat tozsaid oxidizing zone; andrecovering. hydrogen free. from nitrogen? from sai'doxidizingzone as the product of theprocess` 7.; A'. process for producing:- `hydrogenfwhich comprises thestepsaof: passing excess steamupwardlythroughzan `oxidizing ;zone in the presence of; nely divided reduced' metalliferous contact material atafvelocity effective to suspendv the nely divided material inapseudo-liquid condition at a-:temperature below about 1100 F; butsufli.- ciently: high such. that hydrogen is produced under'endothermic conditionsat a desired rate byg-thereaction of steam with the contact material and thexcontactmaterial is oxidized, passing oxidized contact material from the oxidizing zone to a rst-reduction-zone, passing carbon monoxidein excess upwardly through the iirst reduction zone. inithe presence. of vthe nely divided oxidized contact material at a velocity eiiectiveto suspend the'contact material in-a pseudo-liquid condition therein at a temperature significantly above the temperature of the oxidizing zone underexothermic conditions such that lthe contact material is reduced by the carbon monoxide which is converted to carbon dioxideand the heat generated therein is suii'icient: to constitute the principal source of heatifor. the oxidizing zone, passing a relatively small proportion of'contact material from the rst reduction zone to a secondreduction zone wherein the contact material is further reduced by the unconverted carbon monoxide from the rst reduction zone at a temperature below about .700 F. but suiiciently high to obtain thev desired rate of reaction, removing an effluent from the second reduction zone comprising carbon .dioxide and substantially free of carbon monoxide, recycling reduced metalliferous contact material to .the said oxidizing zone.` ata. temperature and in an amount suicient to constitute. the principal. source of heat thereto,` at least a portion of the reduced contact material is'recycled from the iirstl reduction zone, and recovering hydrogen from the oxidizing zone as the productor the process.

8. The process of claim '7 in which the metalliferous contact material comprises manganese.

9. The process of claim 7 `in which the vmetal-'- liferous contact material is cobalt.

10.v The process of claim '7 in which the metalliferous contact material comprises cobalt and manganese.

11. The processor claim 7 in'which the metalliferous contact material comprises vanadium.

12. A process for producing hydrogen which comprisesthe steps of passing excess steam upwardly through an oxidizing zone in the presence of vfinely-divided reduced metalliferous material atv aA velocity eiective to suspend said finely-divided material in a pseudo-liquid condition at a temperature below about 1100 F. but sufficiently highV such that hydrogen'is produced under endothermic conditionsfat a desired rate lby the reaction of steam withV said contact material whereby the contact material is oxidized, passing oxidized contact material from y-said'oxidizing zone to `a.

13 -iirst reduction zone, passing carbon monoxide in excess upwardly through said rst reduction zone in the presence of finely-divided oxidized metalliferous contact material at a velocity eective to suspend said finely-divided contact material in a pseudo-liquid condition therein at a temperature at least 100 E'. above the temperature of said oxidation zone under exothermic conditions such that the metalliferous contact material is reduced by carbon monoxide which is converted to carbon dioxide, removing from said rst reduction zone an eiiiuent containing a relatively small proportion of unconverted carbon monoxide and suspended contact material and passing Y same to a separate second low temperature reduction zone in Which the remaining unconverted carbon monoxide from said first reduction zone reduced unreduced metalliferous contact material suspended in the reaction mixture at a temperature below about '700 F. but at a sufiiciently high temperature to obtain the desired rate of reaction, recovering reduced metal oxide from said second reduction zone and returning same to said first reduction zone, removing an eiliuent from said second reduction zone comprising carbon dioxide and substantially free from carbon monoxide, passing reduced metalliferous contact material from said first reduction zone to said oxidation zone in an amount suicient to constitute the principal source of heat to said oxidizing zone, and recovering substantially pure hydrogen from said oxidizing zone as the product of the process.

13. A process for producing hydrogen which comprises the steps of combusting excess coal with air under suitable conditions for the production of a major proportion of carbon monoxide and a minor proportion of carbon dioxide, passing excess steam upwardly through an oxidizing zone in the presence of iinely divided reduced manganese oxide at a Velocity effective to suspend the reduced manganese oxide in a pseudo-liquid condition at a temperature below about 11.00 F. but suhciently high such that hydrogen is produced under endothermic conditions at a desired rate by the reaction of steam with the reduced manganese oxide whereby the reduced manganese oxide is oxidized, passing the oxidized manganese oxide from the oxidizing zone to the first reduction zone, passing carbon monoxide produced in the combustion .step in excess upwardly through the rst reduction zone in the presence of nely divided oxidized manganese oxide at a velocity eiective to suspend the oxi- 'dized manganese oxide in a pseudo-liquid condition therein at a temperature of at least about 200 F. above the temperature of the oxidizing zone under exothermic conditions such that the oxidized manganese oxide is reduced by carbon monoxide which is converted to carbon dioxide, passing a relatively small proportion of partially reduced manganese oxide to a second reduction zone wherein it is further reduced by the unconverted carbon monoxide from the first reduction zone at a temperature below about 700 F. but suihciently high to obtain the desired rate of reaction, removing an efliuent from the second reduction zone comprising carbon dioxide and substantially free of carbon monoxide, recycling reduced manganese oxide to the said oxidizing zone at a temperature and in an amount suicient to constitute thep rincipal source of heat thereto, at least a portion of the reduced manganese oxide is recycled from the rst reduction zone, and recovering hydrogen from the oxidizing zone as the product of the process.

WILLIAM B. JOHNSON.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,449,635 Barr Sept. 12, 1948 Y FOREXGN PATENTS Number Country Date 220,676 Great Britain Aug. 21, 1924 586,914 Great Britain Apr. 8, 1947 OTHER REFERENCES Morgan, American Gas Practice, vol. I, pages 'l0-74.

Ellis, Hydrogenation of Organic Substances, 3d Edition, pages '715-718.l 

1. A PROCESS FOR PRODUCING HYDROGEN WHICH COMPRISES COMBUSTING CARBON CONTAINING MATERIAL WITH OXYGEN CONTAINING GAS UNDER CONDITIONS SUITABLE FOR THE PRODUCTION OF A MAJOR PROPORTION OF CARBON MONOXIDE AND A MINOR PROPORTION OF CARBON DIOXIDE, PASSING EXCESS STEAM UPWARDLY THROUGH AN OXIDIZING ZONE IN THE PRESENCE OF FINELY DIVIDED REDUCED METALLIFEROUS CONTACT MATERIAL AT A VELOCITY EFFECTIVE TO SUSPEND THE CONTACT MATERIAL IN A PSEUDO-LIQUID CONDITION AT A TEMPERATURE BELOW ABOUT 1100* F. BUT SUFFICIENTLY HIGH SUCH THAT HYDROGEN IS PRODUCED UNDER ENDOTHERMIC CONDITIONS AT A DESIRED RATE BY THE REACTION OF STEAM WITH THE CONTACT MATERIAL AND THE CONTACT MATERIAL IS OXIDIZED, PASSING OXIDIZED CONTACT MATERIAL FROM THE OXIDIZING ZONE TO A FIRST REDUCTION ZONE, PASSING CARBON MONOXIDE WHICH IS PREPARED FROM COMBUSTING CARBON CONTAINING MATERIAL IN EXCESS UPWARDLY THROUGH SAID FIRST REDUCTION ZONE AT A VELOCITY EFFECTIVE TO SUSPEND THE OXIDIZED CONTACT MATERIAL IN A PSEUDOLIQUID CONDITION THEREIN AT A TEMPERATURE SIGNIFICANTLY ABOVE THE TEMPERATURE OF SAID OXIDIZING ZONE UNDER EXOTHERMIC CONDITIONS SUCH THAT THE METALLIFEROUS CONTACT MATERIAL IS REDUCED BY THE CARBON MONOXIDE WHICH IS CONVERTED TO CARBON DIOXIDE AND THE HEAT GENERATED THEREIN IS SUFFICIENT TO CONSTITUTE THE PRINCIPAL SOURCE OF HEAT FOR THE OXIDIZING ZONE, PASSING A RELATIVELY SMALL PROPORTION OF CONTACT MATERIAL FROM THE FIRST REDUCTION ZONE TO A SECOND REDUCTION ZONE WHEREIN THE CONTACT MATERIAL IS FURTHER REDUCED BY THE UNCOVERED CARBON MONOXIDE FROM THE FIRST REDUCTION ZONE AT A TEMPERATURE BELOW ABOUT 700* F. BUT SUFFICIENTLY HIGH TO OBTAIN THE DESIRED RATE OF REACTION, REMOVING AN EFFLUENT FROM THE SAID SECOND REDUCTION ZONE COMPRISING CARBON DIOXIDE AND SUBSTANTIALLY FREE OF CARBON MONOXIDE, RECYCLING REDUCED METALLIFEROUS CONTACT MATERIAL TO THE SAID OXIDIZING ZONE AT A TEMPERATURE AND IN AN AMOUNT SUFFICIENT TO CONSTITUTE THE PRINCIPAL SOURCE OF HEAT THERETO, AT LEAST A PORTION OF THE REDUCED CONTACT MATERIAL IS RECYCLED FROM THE FIRST REDUCTION ZONE, AND RECOVERING HYDROGEN FROM THE OXIDIZING ZONE AS THE PRODUCT OF THE PROCESS. 